Digital Commons Network^™

Addressing The Threat Of Multidrug Resistant Infectious Diseases By Synthesis Of Novel Aminoglycoside Antibiotics, Girish Chandra Sati

Wayne State University Dissertations

The ever-growing increase in multidrug resistant infectious diseases is one of the major cause of human mortality, and there is an inherent need for the development of new antibiotics. Since the discovery of streptomycin, AGAs have been playing a very important role in human therapy as highly potent broad-spectrum antibiotics and are listed as one of the critically important antimicrobials by WHO. AGAs act by inhibiting the bacterial protein synthesis and by targeting the A-site present in the small subunit of bacterial ribosome. The clinical use of AGAs is somewhat restricted due to their toxic effects (ototoxicity and nephrotoxicity) and …

Palladium-Catalyzed Carbonyl Allylation Reactions Using Tin Chloride: A Mini-Review, Armando M. Guidote Jr, Mikael John A. Baltazar, Roy Kristian C. Yanela, Noriyuki Suzuki

Chemistry Faculty Publications

The treatment of allylic alcohols as synthons of carbanions for carbonyl allylation reactions in the presence of a Pd-SnCl2 system has been one of the most interesting and most useful developments demonstrated by Yoshiro Masuyama and co-workers in the field of organic synthesis. The reaction makes use of palladium as an effective catalyst and tin (II) chloride as a low-valent reducing agent which also effectively transforms the allylic group to a nucleophilic group. The organic, as well as organometallic, chemistry of how the transformations occur and how the metals take part in the reaction is of great interest. These could …

Transplanting A Bacterial Immune System: Determining The Function Of A Novel Crispr System, Riannon Smith, Melena Garrett

Research on Capitol Hill

CRISPR (Clusters of Regularly Interspaced Short Palindromic Repeats) loci and cas (CRISPR-associated) genes provide adaptive immunity (see panel below) in bacteria and have recently been repurposed for genome editing.

Systems are structurally and functionally diverse.

• 2 classes, 6 types, 33 subtypes
• Very few have been studied experimentally
• None of the Type IV systems have been characterized

Presence Of Cofactor Nadph Slows Down The Dissociation Of Methotrexate From Dihydrofolate Reductase From Bacillus Stearothermophilus, Ryan Seamus Foley

Theses, Dissertations and Culminating Projects

The goal of this project was to study the effect of the presence or absence of the cofactor NADPH on the binding and release of ligand methotrexate (MTX) to/from Bacillus stearothermophilus (Bs) dihydrofolate reductase (DHFR). A previously developed, fluorescently-labeled Bs DHFR (C73A/S131CMDCC DHFR) was used to investigate the kinetics and protein conformational motions associated with the binding of NADPH and the binding of methotrexate to the holoenzyme. This Bs DHFR contains a distal cysteine where the fluorophore, N-[2-(1-maleimidyl)ethyl]-7-(diethylamino)coumarin-3-carboxamide (MDCC) can be covalently attached. This probe is sensitive to the local molecular environment, reporting on changes in the protein conformation associated …

Stargazin And Gamma-4 Slow The Rate Of Channel Opening And Closing Of Glua4 Ampa Receptors, Vincen David Pierce

Legacy Theses & Dissertations (2009 - 2024)

The ionotropic glutamate receptors are localized in the pre- and postsynaptic membrane of neurons, and they mediate the majority of the fast excitatory synaptic transmission. These receptors are divided into three subtypes: α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA), kainic acid, and N-methyl-D-aspartic acid (NMDA) receptors. AMPA receptor properties are critically dependent on the presence of auxiliary transmembrane proteins, such as transmembrane AMPA receptors regulatory proteins (TARPs). TARPs are the most widespread and well-studied family of auxiliary proteins. For example, the co-assembly of TARPs with AMPA receptors increases the affinity for glutamate, and reduces voltage-dependent blockade by cytoplasmic polyamines in AMPA receptors that lack …

Differentiation Of Potential False Positives From Human Saliva Using Raman Spectroscopy For Forensic Purposes, Selina Casadei

Legacy Theses & Dissertations (2009 - 2024)

Traces of body fluids can be found at a crime scene. Being able to identify and differentiate the body fluids while preserving DNA is fundamentally important for forensic applications. Saliva is an important body fluid that can be found on bite marks, cigarette butts, and more, being an excellent source for DNA extraction. Current tests for saliva and other body fluids are destructive and body fluid specific, and are prone to false positives. Our laboratory has developed a universal method for identification of all main body fluids; saliva, semen, sweat, peripheral blood, and vaginal fluid, using Raman spectroscopy combined with …

Technology Development For Detection Of Circulating Disease Biomarkers From Liquid Biopsies Using Multifunctional Nanomaterials, Mustafa Balcioglu

Legacy Theses & Dissertations (2009 - 2024)

Despite the advance health care, devastating health conditions such as cancer and infectious diseases that affect populations worldwide are too often not diagnosed until morbid symptoms become apparent in the late phase. Obtaining an early and accurate diagnosis that reveal a hidden lethal threat before the disease becomes complicated may dramatically reduce the severity of its impact on the patient’s life and increase the probability of survival. For example, in the case of ovarian cancer, which is the fifth most common malignancy and the fifth leading cause of cancer mortality in women in the US, the 5-year relative survival is …

A Consideration Of Ancient Residues And Their Analysis, Jennifer A. Cardinal

Legacy Theses & Dissertations (2009 - 2024)

Identification of specific use(s) of ancient pottery vessels through empirical verification is currently very limited for archaeological investigations. Although we can postulate a range of purposes or functions for certain vessels, empirical confirmation of actual use has been determined only for a minuscule portion of the available vessels. This thesis will provide a broad review of organic analyses as applied to foodstuff residues left on ancient artifacts as well as discuss several considerations for such analysis that are unique to their application to archaeological specimens.

Dna Functionalized Nanoparticles In Nanobiosensor And Sensor Array Development For Molecular Diagnostics And In Vitro Identification Of Biomolecules, Mustafa Salih Hizir

Legacy Theses & Dissertations (2009 - 2024)

Nucleic acid technology along with vast variety of nanomaterials has demonstrated a great potential in many applications from biosensing studies to molecular diagnostics, from biomedical and bioanalytical research to environmental analysis. Especially short single stranded (ss) DNA molecules, called oligonucleotides, are extraordinary biopolymers featuring diverse functionality on the nanoparticles thanks to their high degree of programmability, target-specific binding or cleavage, molecular recognition ability, structure-switching capability, and unique interactions at the bio-nano interfaces. Among those, there have been many biosensing applications utilizing ss DNAs and numerous nanomaterials through various detection techniques such as fluorometric, colorimetric or electrochemical methods. Although many groundbreaking …

Synthesis And Base Pairing Studies Of 5-Cyanomethyl Uridine (Cnm⁵U) And 5-Cyano Uridine (Cn⁵U) In Rna Duplex, Hsu-Chun Tsai

Legacy Theses & Dissertations (2009 - 2024)

RNA plays an essential role in many biological processes by acting as both genetic information carriers, catalyst and regulator. Natural RNAs usually contain nucleoside analogs from the four common ribonucleosides. There are over 150 chemical modification have been discovered in natural RNA molecules. 5-cyanomethyl uridine is a native modification that has been discovered in total tRNAs from Haloarcula marismortui. This modification in the anticodon wobble position affects the codon recognition, and leads the mutant tRNA to bind not only to AUA but also to AUU and AUG. We synthesized 5-cyanomethyl uridine (cnm5U) and its derivative 5-cyanouridine (cn5U), which has the …

The Development Of Bioaffinity-Based Concepts For On-Site Forensic Analyses : Blood, Sweat, And ... Fingerprints?, Crystal Huynh

Legacy Theses & Dissertations (2009 - 2024)

There have been many advances in forensic science over the recent years, but a majority of the tests currently preformed are still heavily reliant upon laboratory-based processes. This means that valuable pieces of information are left unexamined until a crime scene has been completely processed and evidence is moved to a crime lab. In some cases, the evidence may even be left in a queue due to backlogs from previous cases. The delay resulting from the time necessary for crime scene processing and transportation, as well as additional time spent waiting on lab equipment availability, hinders an investigator’s ability to …

Chemically And Biologically Responsive Nanoparticle Systems For Biomarker Detection And Combination Cancer Therapy, Neil M. Robertson

Legacy Theses & Dissertations (2009 - 2024)

The uniqueness and expression of miRNAs as biomarkers in certain cancers has the potential to radically alter the detection, and therefore the treatment, of the disease. Not only are current detection methods time consuming, and not sensitive enough for biomedical applications, but these small RNAs have yet to be fully utilized in treatment. By utilizing different nanomaterials we aimed to create novel nanodevices for the early, sensitive and specific detection of these biomarkers in a minimally invasive way and develop dual drug releasing nanoparticles, which are entirely controllable, to aid in the treatment of resistant cancer phenotypes.

Carborane Functionalized Cysteine : Synthesis, Structural Characterization, And Biological Evaluation For Boron Neutron Capture Therapy, Tianyu He

Legacy Theses & Dissertations (2009 - 2024)

Carbon-containing boranes, also known as carboranes, have attracted immense interest since their discovery in the 1950’s. Characterization of carboranes revealed their highly symmetrical polyhedral structures, which make them chemically and thermally stable. Their unique chemical properties, hydrophobicity and aromaticity also make them ideal candidates for a variety of applications. Prominent among these are the applications in materials and medicinal chemistry. On the materials chemistry front, carboranes have been investigated as self-assembly building blocks, liquid crystals and gas storage and separation materials. In the medicinal chemistry field, carborane derivatives have been extensively investigated as potential drugs, with a lot of attention …

Genetically Engineered Polypeptides As Biomimetic Light Harvesting Optical Antenna, Jason P. Seeley

Legacy Theses & Dissertations (2009 - 2024)

Natural resources useful for the generation of energy are limited. The development of efficient materials capable of utilizing the abundant free solar radiation is of considerable interest. Utilization of otherwise wasted energy sources, including solar radiation, is a progressive step in the quest for sustainable energy. Solar radiation incident upon the earth’s surface exceeds current energy requirements and motivates scientists to investigate and develop functional devices and nanomaterials including light harvesting complexes (LHC) capable of capturing solar radiation for energy conversion and storage.

Magnetic Assembly Of Soft Robots With Hard Components, Sen Wai Kwok, Stephen A. Morin, Bobak Mosadegh, Ju-Hee So, Robert F. Shepherd, George M. Whitesides

Department of Chemistry: Faculty Publications

Reconfigurable soft robotic actuators with hard components are described. Magnetic attraction is used to couple flexible molded bodies capable of actuation upon pressurization with other flexible molded bodies and/or with hard components (e.g., frames and connectors) to form a seal for fluidic communication and cooperative actuation. Pneumatic decoupling chambers built into the hard components to decouple the hard components from the magnetically-coupled soft molded bodies are described. The use of magnetic self- alignment coupling and pneumatic de-coupling allows for the remote assembly and disassembly of complex structures involving hard and soft components. The magnetic coupling allows for rapid, reversible reconfiguration …

Development Of A Molecularly Imprinted Polymer-Based Electrochemical Sensor For Tyrosinase, Aysu Yarman

Turkish Journal of Chemistry

For the first time a molecularly imprinted polymer (MIP)-based sensor for tyrosinase is described. This sensor is based on the electropolymerization of scopoletin or o-phenylenediamine in the presence of tyrosinase from mushrooms, which has a high homology to the human enzyme. The template was removed either by treatment with proteinase K or by alkaline treatment. The measuring signal was generated either by measuring the formation of a product by the target enzyme or by evaluation of the permeability of the redox marker ferricyanide. The o-phenylenediamine-based MIP sensor has a linear measuring range up to 50 nM of tyrosinase with a …

Synthesis, Solvatochromism, And Biological Activity Of Novel Azo Dyes Bearing 2-Pyridone And Benzimidazole Moieties, Dusan Mijin, Biljana Bozic Nedeljkovic, Bojan Bozic, Ilijana Kovrlija, Jelena Ladarevic, Gordana Uscumlic

Turkish Journal of Chemistry

New azo dyes bearing 2-pyridone and benzimidazole moieties were prepared using diazotization of 4-(1H-benzo[d]imidazol-2-yl)aniline and coupling of the obtained diazonium salt with substituted 3-cyano-2-pyridones. Obtained compounds were characterized via UV-Vis, FT-IR, and $^{1}$H and $^{13}$C NMR spectroscopy as well as by elemental analysis data. The UV-Vis spectra of the synthesized dyes were measured in thirteen solvents of different properties at room temperature. Solvatochromism and tautomerism of novel azo dyes were discussed. An MTT (3,4,5-dimethyl-thiazol-2-yl)-2,5-diphenyl tetrazolium bromide) test was performed to prove the biocompatibility of the investigated dyes. The investigated dyes exhibited satisfying antiproliferative activities against both tumor cell lines, MDA-MB-231 …

Development Of A Nanoscale-Based Optical Chemical Sensor For The Detection Of No Radical, Özlem Öter, Aki̇f Ci̇han Aydin, Merve Zeyrek Ongun, Erdal Çeli̇k

Turkish Journal of Chemistry

Nitric oxide is one of the most important biochemical parameters in biological processes; it is also known as carcinogenic. There is need for the design of stable and durable solid phase nitric oxide sensors. In this study, we immobilized the nitric oxide sensitive molecules pyrene, tris(2,2'-bipyrdyl)dichlororuthenium(II) hexahydrate (Ru(bipy)$_{3}^{2+})$, and magnesium phthalocyanine (Mg-Pc) for the first time in polymeric or glassy matrices. We applied silver nanoparticles and ionic liquids in the fabrication process of polymeric electrospun fibers and thin films. We compared their NO sensitivity in micelle solutions that mimic the cell medium by both steady state and lifetime-based fluorescence measurements. …

Use Of Calcined Layered Double Hydroxide [Zn$_{2}$-Al-Co$_{3}$] For Removal Of Textile Dye Acid Green 1 From Wastewater: Kinetic, Equilibrium, Comparative, And Recycling Studies, El Hassane Mourid, Mohamed Lakraimi, Souad El Abridi, Lhaj Benaziz, El Hassan Elkhattabi, Moha Berraho

Turkish Journal of Chemistry

In the present study, calcined layered double hydroxides (CLDHs) were obtained by heating [Zn$_{2}$-Al-CO$_{3}$] at 500 $^{\circ}$C. The adsorption of the textile dye acid green 1 (AG1) by CLDH was carried out at different pH levels, adsorbent--adsorbate contact times, and AG1/CLDH mass ratios. Equilibrium at room temperature was reached after 24 h, which was confirmed by the kinetic modeling of the experimental data by the pseudo-second-order model. The adsorption is described by a Langmuir-type isotherm. The comparative study of adsorption isotherms in calcined and uncalcined phases reveals that the former could be a good candidate for trapping such pollutants. After …

Teaching Chemistry In A Spiral Progression Approach: Lessons From Science Teachers In The Philippines, Joymie R. Orbe, Allen A. Espinosa, Janir T. Datukan

Australian Journal of Teacher Education

As the Philippines moves towards implementing the K-12 curriculum, there has been a mismatch in teacher preparation in science. The present teacher education curriculum prepares science teachers to specialise in a specific field (e.g. integrated science, biology, chemistry, and physics). However, in the K-12 curriculum, they are required to teach all the sciences in a spiral progression approach. Hence, this study analysed the experiences of science teachers in teaching chemistry in the K-12 curriculum in order to identify their challenges and how they are overcoming them. Findings suggest that the teacher’s content, pedagogy, and assessment in chemistry are problematic; specifically, …

Poly L-Dopa/Poly(Ethylenedioxythiophene) As A Novel Mussel-Inspired Electroactive Binder For Environmentally Friendly Hybrid Supercapacitors, Elham Heydaripour, Mohammad Reza Nateghi, Mohammad Hossein Mosslemin

Turkish Journal of Chemistry

3,4-Dihydroxy-L-phenylalanine and ethylenedioxythiophene were chemically copolymerized via an oxidative process in aqueous solution. The copolymer was used as a novel mussel-inspired electroactive binder in conjunction with a nickel-based metal organic frame work for fabrication of environmentally friendly supercapacitors. The binder, in addition to the sticking effect, contributes to electric charge storing via the redox process of catechol moieties of poly(3,4-dihydroxy-L-phenylalanine) and also the formation of a high charge-storing double layer due to the presence of poly(ethylenedioxythiophene). Cyclic voltammetry, charge/discharge measurements, and electrochemical impedance spectrometry showed that the hybrid supercapacitors based on Ni-benzidine MOF with the new electroactive binder exhibit very …

Richard Smalley And The Materials Of Tomorrow: The Discovery And Science Of Fullerenes, Creighton A. Jackson

Natural Sciences Student Research Presentations

This poster for the Natural Sciences Poster Session at Parkland College details the contributions of Richard Smalley to organic chemistry, specifically the discovery of fullerenes in 1984, which led to advancements in the field of nanoscience. Fullerene use in materials science, Single-walled and multi-walled nanotubes and use of fullerenes in biology are also outlined.

Richard Smalley And The Materials Of Tomorrow: The Discovery, Properties, And Science Of Fullerenes, Creighton A. Jackson

Natural Sciences Student Research Presentations

These are slides accompanying a presentation given at the Natural Sciences Poster Session at Parkland College outlining the properties of and ongoing research pertaining to fullerenes in materials science.

Mechanistic Studies Of Proton-Coupled Electron Transfer Reactions Involving Antioxidants, Kejie Meng

Theses and Dissertations

The objective of the research was to investigate proton-coupled electron transfer (PCET) reactions involving antioxidants to gain insight into the detailed mechanisms of glutathione (GSH), Trolox, and α-tocopherol (α-TOH). PCET reactions are complex redox reactions that transfer electrons and protons sequentially or in concert. These reactions are ubiquitous in natural or artificial processes that produce electrochemical energy that is extractable as electricity or as chemical fuels of high energy content. Examples of processes based on PCET are photosynthesis, respiration, nitrogen fixation, carbon dioxide reduction, redox fuel cells, and artificial photosynthesis. Antioxidants were selected as a PCET model to understand the …

Chemical And Physical Studies Of Charge Transfer Excited States Of Ruthenium Complexes With Aromatic Ligands, Marim Khalifa Alnaed

Wayne State University Dissertations

The 3MLCT excited states generated from tris-bipyridineruthenium(II), [Ru(bpy)3]2+ and related complexes was ionized by 405 nm irradiation in ambient, acidic aqueous solutions. The photoionization product was Ru(bpy)3]3+ and an electron with a quantum yield of about 0.040.02 in 0.5 M acid. However, 532 nm radiation does not induce photoionization, and it generates the 3MLCT excited state that can be photoionized by 405 nm irradiation. The proton is a very good electron scavenger, and the rate of phoionization of the 3MLCT excited state was determined to be acid dependent and it increased about ten-fold for acid concentrations beween 0.001 and 4 …

Harnessing Radical Reactivity For The Construction Of Natural Product Frameworks And Transition Metal Catalyst Stability In A Modified Kochi Coupling Reaction, Mathes Hewage Hansamali Sakuntala Sirinimal

Wayne State University Dissertations

Polycyclic N-containing heterocycles play an important role in therapeutic

applications and as molecular tools in studying biological processes, making them

important synthetic targets. Current synthetic approaches are too lengthy, use toxic

reagents or are limited to accessing a particular framework and hence, their synthesis

warrant further study. We have recently developed conditions to avoid both reduction and

slow addition in aminyl radical cyclizations in our venture to access the constrained ABC

core of calyciphilline A, a Daphniphyllum alkaloid. An electron deficient enone with a

pendent internal alkyne as the neutral aminyl radical precursor was used for radical

cyclization. Based on …

Synthesis And Kinetic Activity Analysis Of Substituted Pyrazole, Pyrazoline, And Pyrazolidine Alcohol Dehydrogenase Inhibitors, Meagan E. Hackey

Chemistry Theses

Alcohol dehydrogenase inhibitors may be employed for the treatment of parasitic infection in humans. A series of substituted pyrazoline derivatives were synthesized to elucidate the pharmacophore for the inhibition of ADH. Targeted structure modification was used to alter the electronic and steric interactions associated with the enzyme active site. This study identified several effective N-aryl-carboxamide derivatives with horse liver ADH inhibition, comparable to that of 4-methylpyrazole, a known ADH inhibitor. The identification of pharmacophoric regions will allow for the methodological modification of these compounds to improve enzyme affinity and targeted inhibition. Future research may include additional solubility, toxicity and …

Recent Progress In The Synthesis Of Six-Membered Aminocyclitols (2008-2017), William A. Donaldson

Chemistry Faculty Research and Publications

Aminocyclitols are of interest as glucosidase inhibitors, as probes for the study of pseudoglycosyltransferases, and as potential therapeutics for the treatment of Gaucher’s disease. The synthesis of these targets was reviewed in early 2008, and the aim of this review is to cover material relevant to the synthesis of aminocyclitols since that time. While not a focus of this review, biological evaluation of compounds will be presented where it is recorded in the literature.

Synthesis Of 5-Methyl-3-Phenyl-1,3,4-Oxadiazol-2(3h)-One Derivatives By Electrophilic Aromatic Substitution, Amanda Solis Conde

Browse all Theses and Dissertations

An important research element in the Turnbull laboratory has been the one-pot synthesis of 5-methyl-3-phenyl-1,3,4-oxadiazol-2(3H)-one from sydnone. The present study reexamined the reaction of 5-methyl-3-phenyl-1,3,4-oxadiazol-2(3H)-one with electrophiles and optimized methods for synthesis of oxadiazolinone derivatives. Further the oxadiazolinone derivatives were reacted with electrophiles to better comprehend the donating ability of the oxadiazolinone ring system in general with the expectation that the oxadiazolinone ring system is a slightly donating system. Additionally, when the structure assignment of the oxadiazolinone derivative was ambiguous, the corresponding oxadiazolinone or it’s isomer was synthesized from the appropriate sydnone to validate or refute the suggested structure. The …

Electrochemical Investigation Of The Kinetics Of Chloride Substitution Upon Reduction Of [Ru(Porphyrin)(No)Cl] Complexes In Thf., Jeremy R. Zink, E G. Abucayon, Anthony R. Ramuglia, Arghavan Fadamin, James E. Eilers, George B. Richter-Addo, Michael J. Shaw

SIUE Faculty Research, Scholarship, and Creative Activity

The electrochemistry of several ruthenium porphyrin nitrosyl chloride complexes [Ru(por)(NO)Cl] have been examined in tetrahydrofuran. The complexes undergo 1-electron irreversible reductions which result in the diffusion-limited substitutions of the chloride ligands for THF. This chloride metathesis is reversible in the presence of added NBu₄Cl, and equilibrium constants and rate constants for chloride loss have been estimated. These parameters correlate with the NO stretching frequencies of the parent complexes, with more electron-donating porphyrin ligands favouring chloride loss from the reduced complexes. The [Ru(por)(NO)(THF)] products of the reductions can be detected by IR, EPR and visible spectroscopies. These species undergo …